Auras 2004 An Overview of Polylactides As Packaging Materials

Review 835
Summary: Polylactide polymers have gained enormous interact with aromatic hydrocarbons, ketones, esters, sulfur
attention as a replacement for conventional synthetic pack- compounds or water. The CO2, O2 and water permeability
aging materials in the last decade. By being truly biodegrad- coefficients of PLA are lower than those of PS and higher than
able, derived from renewable resources and by providing those of PET. Its barrier to ethyl acetate and D-limonene is
consumers with extra end-use benefits such as avoiding comparable to PET. The amount of lactic acid and its deriv-
paying the ‘‘green tax’’ in Germany or meeting environ- atives that migrate to food simulant solutions from PLA is
mental regulations in Japan, polylactides (PLAs) are a grow- much lower than any of the current average dietary lactic acid
ing alternative as a packaging material for demanding intake values allowed by several governmental agencies.
markets. The aim of this paper is to review the production Thus, PLA is safe for use in fabricating articles for contact
techniques for PLAs, summarize the main properties of PLA with food.
and to delineate the main advantages and disadvantages of
PLA as a polymeric packaging material. PLA films have
better ultraviolet light barrier properties than low density
polyethylene (LDPE), but they are slightly worse than those
of cellophane, polystyrene (PS) and poly(ethylene terephtha-
late) (PET). PLA films have mechanical properties compar-
able to those of PET and better than those of PS. PLA also has
lower melting and glass transition temperatures than PET and
PS. The glass transition temperature of PLA changes with
time. Humidity between 10 and 95% and storage temper-
atures of 5 to 40 8C do not have an effect on the transition
temperature of PLA, which can be explained by its low water
sorption values (i.e. <100 ppm at Aw ¼ 1). PLA seals well at
temperatures below the melting temperature but an appreci-
able shrinking of the films has been noted when the material is
sealed near its melting temperature. Solubility parameter
predictions indicate that PLA will interact with nitrogen Percent transmission versus wavelength for PLA(98% L-
compounds, anhydrides and some alcohols and that it will not lactide), PS, LDPE, PET and cellophane films.
An Overview of Polylactides as Packaging Materials

Rafael Auras,* Bruce Harte, Susan Selke
The School of Packaging, Michigan State University, East Lansing, MI 48824-1223, USA
Fax: þ1 (517) 353-8999; E-mail: aurasraf@msu.edu
Received: April 8, 2004; Revised: June 18, 2004; Accepted: June 28, 2004; DOI: 10.1002/mabi.200400043
Keywords: barrier; biodegradable; diffusion; permeability; polylactides
Introduction obtained from a renewable agricultural source (corn);[25–27]

(2) its production consumes quantities of carbon dioxide;[4]
Polylactide (PLA), a polymer derived from lactic acid (2- (3) it provides significant energy savings;[28] (4) it is
hydroxy propionic acid), has been widely studied for use in recyclable and compostable;[23,29,30] (5) it can help improve
medical applications because of its bioresorbable and farm economies and (6) the physical and mechanical
biocompatible properties in the human body.[1–16] Due to properties can be manipulated through the polymer
its higher cost, the initial focus of PLA as a packaging architecture.[31–38] Figure 1 shows a life cycle model for
material has been in high value films, rigid thermoforms, polylactide polymers.
food and beverage containers and coated papers. PLA Early economic studies showed that PLA is an economic-
may have packaging applications for a broader array of ally feasible material to use as a packaging polymer.[24,27,28]
products[17–22] as modern and emerging production tech- Medical studies have shown that the level of lactic acid
nologies lower its production costs.[17,18,23,24] The produc- (LA) that migrates to food from packaging containers is
tion of PLA presents numerous advantages: (1) it can be much lower than the amount of LA used in common food
Macromol. Biosci. 2004, 4, 835–864 DOI: 10.1002/mabi.200400043 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
836 R. Auras, B. Harte, S. Selke
ingredients.[40] Therefore, polymers derived from lactic acid simplest hydroxyl acid with an asymmetric carbon atom
may be good candidates for packaging applications.[3,4,17,18] and it exists in two optically active configurations, the L(þ)
By providing consumers with extra end-use benefits, and D() isomers. The L(þ) and D() isomers are produced
such as avoiding paying a ‘‘green tax’’ in Germany or in bacterial systems. Mammalian systems produce only the
meeting environmental regulations in Japan, PLA has L(þ) isomer which is easily assimilated. Scheme 1 shows
become a growing alternative as a packaging material for the chemical structure of the L and D lactic acids.
demanding markets.[41] Currently, PLA is being used as a The majority of lactic acid is made by bacterial fer-
food packaging polymer for short shelf life products with mentation of carbohydrates. The fermentation processes to
common applications such as containers, drinking cups, obtain lactic acid can be classified according to the type of
sundae and salad cups, overwrap and lamination films and bacteria used. In the Heterofermentative method less than
blister packages.[42–44] Moreover, new applications include 1.8 moles of lactic acid per mole of hexose is produced
thermoformed PLA containers being used in retail markets along with significant levels of other metabolites such as
for fresh fruit and vegetables.[44,45] acetic acid, ethanol, glycerol, mannitol and carbon dioxide.
In the Homofermentative method an average of 1.8 moles of
lactic acid per mole of hexose and minor levels of other
Polylactide Production
metabolites are produced. This conversion yields 90þ g
The basic constitutional unit of PLA, lactic acid, can be lactic acid per 100 g glucose. Since homofermentative
manufactured by carbohydrate fermentation or chemical pathways lead to greater yields of lactic acid and lower
synthesis. Lactic acid (2-hydroxy propionic acid) is the levels of byproducts, homofermentative pathways are
Rafael A. Auras is a Research Associate at the School of Packaging, MSU, East Lansing, MI, USA. He
holds a BSChE from the National University of Misiones, Argentina, a MS in Materials Science and
Technology from the National University of San Martin, Buenos Aires, Argentina, and a Ph.D. in
Packaging Science from the School of Packaging, MSU. Dr. Auras taught courses in materials science,
polymers, and shelf life. His current research focuses in edible and biodegradable polymers, mass
transfer phenomenon in polymers, food product/package compatibility and interaction, and package
sustainability. Dr. Auras has been a Fulbright, CONICET, and AECI fellow. He is an active member in
the polymer and the packaging fields.
Dr. Bruce R. Harte is Professor at the School of Packaging, Michigan State University, and an Adjunct
Professor in the Department of Food Science and Human Nutrition. He has been a member of the
packaging faculty since January, 1979, and was Director of the School 1993–2004 (April). He teaches a
variety of courses, including food packaging, packaging development, and paper based packaging. His
research interests include materials applications to packaging, product/package interaction and
compatibility, product stability, barrier packaging and active packaging. Dr. Harte has had substantial
interaction with the packaging and manufacturing industries, both in the US and internationally. He has
substantial international experience, having organized and delivered short courses in Morocco, Mexico,
Brazil, S. Korea, and Peru among others. He was a board member of the International Association of
Packaging Research Institutes from 1993–2003. His awards include the following: Institute of Food
Technologists, Food Packaging Division, Reister-Davis Award for Outstanding Achievement in
Food Packaging, 2001; National Institute of Packaging, Handling, and Logistics Engineers, The John
C. Wilford Memorial Award for Outstanding Achievement in Packaging, 2001; Institute of Packaging
Professionals; Selected as a ‘‘Fellow’’ in Recognition of Outstanding Professional Achievement
and Service to the Field of Packaging, 2001; MSU Packaging Alumni Association Hall of Fame
Inductee, 2003.
Susan E. Selke is a Professor in the School of Packaging at Michigan State University, where she has
taught for 20 years. She holds MS and PhD degrees in Chemical Engineering from Michigan State. Her
research interests include plastics, environmental issues, recycling, barrier properties, active packaging,
applications of electronic nose technology, VCI materials, and tamper-evident and child resistant
packaging. She teaches courses on plastics packaging, packaging and the environment, and analytical
solutions to package design. Dr. Selke has authored or coauthored a variety of publications, including
books on packaging and the environment and on plastics packaging, and a forthcoming textbook on
paper and wood packaging.
Macromol. Biosci. 2004, 4, 835–864 www.mbs-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
An Overview of Polylactides as Packaging Materials 837
Scheme 1. Chemical structure of L and D-lactic acid (m.p. is

melting point).
h1. If the lactic acid is used in pharmaceutical and food

derivative products, it should be purified via distillation.
High molecular weight PLA can be obtained using
different routes (see Scheme 2). The chemical synthesis
route can be used to produce large scale quantities of
racemic lactic acid[47] but it is economically unviable. As a
Figure 1. Life cycle for polylactide polymers, adapted from consequence, the production of L-lactic acid by fermenta-
Hartmann.[39] tion is gaining acceptance. In general, there are three
methods which can be used to produce high molecular mass
PLA of about 100 000 Daltons: (a) direct condensation
mainly used by industry.[46] The majority of the fermenta- polymerization; (b) azeotropic dehydrative condensation
tion processes nowadays use a genus of Lactobacilli which and (c) polymerization through lactide formation. Poly-
yields a high rate of lactic acid. These bacteria are classified merization through lactide formation, patented by Cargill
as homofermentative, and the general processing condi- Inc. in 1992,[23,48] is by and large the current method used
tions include a pH of 5.4–6.4, a temperature of 38–42 8C for producing PLA. Direct condensation polymerization is
and a low oxygen concentration. In general, sources of the least expensive route. However, it is very difficult to
simple sugars such as glucose and maltose from corn or obtain a solvent-free high molecular weight poly(lactic
potato, sucrose from cane or beet sugar and lactose from acid). Therefore, the use of chain coupling agents and
cheese whey are used. In addition to carbohydrates, other adjuvants adds cost and complexity to the process.[47,49–53]
nutrients such as B vitamins, amino acids and nucleotides Azeotropic dehydrative condensation of lactic acid can
are provided by rich corn steep liquor. Generally, batch yield high molecular weight poly(lactic acid) without the
processes produce 1 to 4.5 g L1 h1 of lactic acid while use of chain extenders or adjuvants. The general procedure
continuous processes produce 3 to 9.0 g L1 h1 of lactic consists of reducing the distillation pressure of lactic acid
acid, and cell recycle reactors produce near to 76 g L1 for 2–3 h at 130 8C. The majority of the condensation water
Scheme 2. Synthesis methods for obtaining high molecular weight PLA, adapted from Hartmann.[49]
Scheme 4. Constitutional unit of polylactide.
Scheme 3. Chemical structures of LL-, meso- and DD-lactides

(m.p. is melting point).
unit of –[OCH(CH3)CO–O–CH(CH3)–CO]– is formed by
is then removed. Catalyst is added along with diphenyl ring-opening polymerization of the lactides.[23,46,49,55] The
ester. A tube packed with 3 Å molecular sieves is attached to ring-opening polymerization can be cationic, initiated by
the reaction vessel and the solvent returned to the vessel via methyl trifluoromethanesulfonic acid or trifluoromethane-
the molecular sieves for an additional 30–40 h at 130 8C. sulfonic acid (triflic acid),[54–56] or anionic, initiated by
Finally, the polymer is isolated as is or dissolved and the nucleophilic reaction of the anion with the carbonyl,
precipitated for further purification. Details of this techni- with subsequent acyl-oxygen cleavage.[54,55,57,58] Ex-
que can be found elsewhere.[49] tensive research on the different methods to initiate the
Polymerization through lactide formation is the current ring opening polymerization has been reported else-
method used by Cargill Dow LLC to obtain polylactide where.[49,54–56,58–75] Scheme 4 shows the constitutional
polymers of high molecular weight for commercial unit of PLA polymers.
applications. From dextrose fermentation, either D-lactic Figure 2 shows a schematic presentation of the current
acid, L-lactic acid or a mixture of the two are pre- Cargill Dow LLC PLA production process in Blair,
polymerized to obtain an intermediate low molecular mass Nebraska.
poly(lactic acid), which is then, under lower pressure,
catalytically converted into a mixture of lactide stereo-
isomers.[54] Lactide, the cyclic dimer of lactic acid, is
Polylactide Properties
formed by the condensation of two lactic acid molecules as
follows: L-lactide (two L-lactic acid molecules), D-lactide The properties of high molecular weight PLA are deter-
(two D-lactic acid molecules) and meso-lactide (an L-lactic mined by the polymer architecture (i.e. the stereochemical
acid and an D-lactic acid molecule) (see Scheme 3). makeup of the backbone) and the molecular mass, which is
After vacuum distillation of the lactide, high molecular controlled by the addition of hydroxylic compounds. The
mass PLAwith controlled optical purity and a constitutional ability to control the stereochemical architecture permits
Figure 2. Current production process for PLA, adapted from Gruber.[48]
precise control over the speed of crystallization and finally all PLAs are made up of L- and D,L-lactide copolymers.[76] It
the degree of crystallinity, the mechanical properties and the is known that poly(L-lactide) and poly(D-lactide) form an
processing temperatures of the material. In addition, the equimolar stereocomplex crystalline structure (i.e., rac-
degradation behavior strongly depends on the crystallinity of lactides) having a significantly higher melting temperature
the samples. In this section, the PLA polymer structure, (230 8C) than the homopolymers.
optical, physical, mechanical, rheological, processing, Dimeric polymerization imparts some order to the
solubility, barrier, and degradation properties are reviewed. otherwise random distribution of L- and D-stereocenters in
The advances achieved in the last few years are reviewed and PLA chains. Hence, the lactide ring-opening polymeriza-
research on PLA blends and composites is briefly described. tion process gives a fundamentally different molecular
architecture for PLA polymers derived from lactic isomeric
mixtures other than 100% L- and 50/50 D,L-lactic acid. High
Structure
molecular weight bulk lactide polymerization should be
Unmodified polylactides are linear macromolecules having conducted at high temperatures (e.g. 190–200 8C) to
a molecular architecture that is determined by their maintain the appropriate viscosity, and at these temper-
stereochemical composition. The repeat unit of PLA atures racemization can become an important side reaction.
(72 g mol1) contains one stereocenter that is either L(S) However, a laboratory scale polymerization of lactide at
or D(R) in configuration. Microorganisms mainly produce low reaction temperature such as 120–140 8C gives a high
L-lactic acid, and no major sources of D-lactic acid are molecular weight PLA.
available, although some lactobacilli are reported to Reactivity among the lactide isomers is slightly different.
produce D-lactic acid.[46] The repeat units are either added meso-Lactide has a higher rate of hydrolysis and a greater
as dimers during the ring-opening lactide polymerization or tendency to polymerize. The L- and D-enantiomers have
are added to the final polymer as lactic acid monomers via identical rates. Witzke[76] attributed this rate difference to a
direct condensation polymerization, as explained in the different configurational and conformational structure. Ener-
previous section. Both mechanisms involve acyl cleavage gy studies indicate that meso-lactide is about 1.7 kcal mol1
of the ester bond with preservation of chirality. meso- more stable than L-lactide. Although not perfect, the
Lactide possesses a two-fold axis of improper rotation and assumption of similar reactivities for lactide production and
is therefore optically inactive. Lactide can be obtained as L,L polymerization is still reasonable, resulting in a small error in
or D,D enantiomers, commonly called L-lactide and D-lactide final composition estimations.[76] Nevertheless, the config-
(which in the Cahn-Ingold-Prelog system are called the urational and conformational differences between meso- and
(S,S) and (R,R) enantiomers, respectively), the meso L-lactide result in different physical properties, such as
compound (R,S), and a racemic or equimolar mixture of melting point, solubility and relative volatility.
the L and D enantiomers, rac-lactide, commonly referred to As far as polymerization is concerned, the role of meso-
as DL-lactide (Scheme 3). The literature sometime confuses lactide is to provide amorphous polylactide when it is
meso- and rac-lactides, and refers to them as DL-lactide. polymerized with L-lactide. Witzke[76] investigated the
In the ring polymerization technique, the lactide stereo- molecular architecture of different lactides and found that
isomers are produced from the depolymerization of low poly(L-lactide) is arranged in a syndiotatic manner. Poly-
molecular weight poly(lactic acid) using tin catalysis and (meso-lactide) has a structural configuration of repeat units
stereoselective initiators to enhance the rate and selectivity of (RS)-(SR)-(RS)-(SR), which is syndiotactic in dimers. It
of the intramolecular cyclization reaction. The molten has also been reported as having an isotactic structure (RS)-
lactide is produced in proportions close to statistical (RS)-(RS)-(RS).
expectations from the initial lactic acid isomers (equal Depending on the preparation conditions, poly(L-lactide)
reactivity), wL-lactide ¼ S2 wD-lactide ¼ R2 wmeso-lactide ¼ 2RS crystallizes in three forms (a, b and g). The stable a-form
where S and R are the original fractions of L-lactic acid and exhibits a well-defined diffraction pattern.[77] Recently,
D-lactic acid, respectively, and w is the weight fraction. Sasaki and Asakura[78] analyzed the a-form of poly-
Since the initial distribution of lactide isomers determines (L-lactide) using linked-atom least squares refinements for
the potential for polylactide crystallization, lactide is X-ray fiber diffraction data, and found that the a-form has
purified by vacuum distillation. PLA derived from greater an orthorhombic P212121 space group, with a unit cell
than 93% L-lactic acid can be semicrystalline whereas PLA containing two antiparallel chains. ‘‘The chain conforma-
from between 50 and 93% L-lactic acid is strictly amor- tion was the 2-fold (15*2/7) helix distorted periodically
phous. Both meso- and D-lactide induce twists in the form of the regular s(3*10/7 helix)’’.[78] The lattice
otherwise very regular poly(L-lactide) molecular architec- parameters were a ¼ 10.66 Å, b ¼ 6.16 Å, and c (chain
ture. Molecular imperfections are responsible for the axis) ¼ 28.88 Å, with a crystal density of 1.26 g cm3.[78]
decrease in both the rate and extent of poly(L-lactide) The b-form can be prepared at a high draw ratio and high
crystallization. Since polylactide production always con- drawing temperature. The chain conformation is a left-
tains some amount of meso-lactide impurities, practically handed 3-fold helix.[77,78] The b form of poly(L-lactic acid)
has an orthorhombic unit cell (containing 6 chains) produce more perfect crystals and higher-melting crys-
containing a 3 l (3 Å rise/1 monomeric unit) polymeric tals.[92] In addition, the composition of the PLA (i.e. the
helix. The unit cell dimensions are as follows: a ¼ 10.31 Å, presence of D- and meso-lactide) can increase the rate of
b ¼ 18.21 Å, c ¼ 9.0 Å.[77] The a-structure is more stable crystallization. PLA is a slowly crystallizing polymer.
than the b-structure, with a melting point of 185 8C Vasanthakumari and Pennings[93] reported that the rate of
compared to 175 8C for the b-structure.[77] Chain packing crystal formation increased with a decrease of the molec-
in the b-form has recently been termed a frustrate structure ular weight. Also, Kolstad,[94] working with poly(L-lactide-
where the crystal structure rests on a frustrated packing of co-meso-lactide) in the range of 0 to 9% meso-lactide, found
three three-fold helices in a trigonal unit-cell of parameters that the crystallization half-time (i.e. the time taken for half
a ¼ b ¼ 10.52 Å, c ¼ 8.8 Å, space group P32.[79] of the lactide to crystallize) increased by around 40% for
The g-form, found by epitaxial crystallization, contains every one percent of meso-lactide in the polymerization
two antiparallel s(3/2) helices in the pseudoorthorhombic mixture. In addition, he reported that the crystallization rate
unit cell (a ¼ 9.95 Å, b ¼ 6.25 Å, c ¼ 8.8 Å) and it assumes was driven mainly by the reduction in melting point of the
the known three-fold helix of polylactides.[80] Table 1 copolymers. Furthermore, talc in the mix acted as a nucle-
shows the unit cell parameters for non-blended PLLA. ating agent, increasing the nucleation density term and
Zell et al.[84] and Thakur et al.[85] used 13C solid-state decreasing the crystallization half-time and the time to
NMR spectroscopy as a tool to determine PLA optical complete crystallization.[94] Quenching also decreases the
purity, crystallinity, morphology and LA isomer distribu- half-time crystallization.[95] Research carried out on blends
tion. Thakur et al.[85] developed a method to deconvolute of PLLA/PDLA containing low concentrations of PDLA
the NMR spectral data and extract information about the have shown it to be more effective as a nucleating agent than
percent of crystallinity and identify the morphology of talc. A maximum nucleation efficiency of 66% was
PLLA. Kasperczyk[86] also used 13C NMR to determine the observed at 15 wt.-% PDLA.[96] Tsuji and Ikada[97] inves-
composition of a series of glycolide/lactide copolymers. tigated the effect of the molecular weight of atactic poly(LD-
Nuclear magnetic resonance data for PLA was reported lactide) (PDLLA) on the crystallization behavior and
by Spinu et al.[87] and L-PLA showed five peaks at 169.27, morphology of isotatic poly(L-lactide) (PLLA). They found
169.31, 169.42, 169.49 and 169.66 ppm. The signal at that the spherulite structure became more disordered as the
169.666 ppm was assigned to the carbonyl carbon of molecular weight of PDLLA increased.[97] They also
successive L-lactic acids. The other four signals are due to reported that a significant depression of the melting tem-
the carbonyl carbons in the polymer chain. In L,D-PLA six perature (Tm) was seen as PLLA was blended with PDLLA,
peaks were reported at 169.136, 169.301, 169.342, 169.400, due to the presence of D-lactide. Also, Baratian et al.[98]
169.548 and 169.569 ppm. The extra peak is attributed to reported that the presence of random copolymers contain-
the way that PLA polymers are produced (i.e. by conden- ing 1.5 to 6% of D-lactide decreased the degree of crystal-
sation or ring opening polymerization, since in condensa- linity and spherulite growth rates.[98,99] Ikada et al.[100]
tion the L- or D-lactic acid are introduced randomly, while in studied the crystallization of the stereocomplex crystallites
ring opening polymerization, they are introduced in pairs). (racemic crystallites) of PDLA and PLLA. When these
PLLA crystals have been grown in different solvents to crystallites have a stoichiometric ratio of 1:1 (L-lactyl unit:
study the morphology and the rate of crystallization. PLLA D-lactyl unit), an increase in the melting temperature of
crystals are highly dependent on the L-concentration. The 50 8C is observed compared to homocrystallites of either
rate and extent of crystallization also depend on the PLLA or PDLA.[60] The eutectic crystallization of PLLA
presence of nucleating agents as well as on the time and with pentaerythrityl tetrabromide was studied by Vasantha-
temperature.[11,57,88–91] Long annealing times at temper- kumari[90] and epitaxial crystallization was investigated by
atures higher than the glass transition temperature (Tg) Cartier et al.[80]
Table 1. Unit cell parameters for non-blended PLLA and stereocomplex crystals, adapted from Tsuji.[11]
Space Group Chain Orientation N. of Helical a b c a b g

helices/ conformation
unit cell nm nm nm deg deg deg
[81]
PLLA a-form Pseudo-orthorhombic – 2 103 1.07 0.645 2.78 90 90 90
PLLA a-form[77] Pseudo-orthorhombic – 2 103 1.06 0.61 2.88 90 90 90
PLLA a-form[82] Orthorhombic Parallel 2 103 1.05 0.61 – 90 90 90
PLLA b-form[77] Orthorhombic – 6 31 1.031 1.821 0.90 90 90 90
PLLA b-form[79] Trigonal Random up-down 3 31 1.052 1.052 0.88 90 90 120
PLLA g-form[80] Orthorombic Antiparallel 2 31 0.995 0.625 0.88 90 90 90
Stereo complex[83] Triclinic Parallel 2 31 0.916 0.916 0.870 109.2 109.2 109.8
Optical
Visible and Ultraviolet Range
The absorption of visible and UV light by polymers is one of
the main factors affecting food quality. The protection of
light sensitive foods such as juices, vitamin and sports
drinks, dairy products and edible oils from UV radiation
when packaged in plastic containers has been widely
investigated.[101–105] For example, light has been found to
affect the flavor and, to a lesser degree, the nutritional
content of milk.[106] Milk is mainly affected by the 400–
550 nm wavelengths[102] but researchers have also reported
that other wavelengths (i.e. UV-B, UV-C and visible) also Figure 3. Percent transmission versus wavelength for PLA(98%
L-lactide), PS, LDPE, PET and cellophane films. (PLA samples
damage the quality of milk.[106] Similar results have been
were obtained from Cargill Dow LLC).
found for juices and edible oils. Therefore, the material used
to produce the primary package is critical in minimizing
product damage. through the films. Therefore, the application of transparent
The transmission of visible and ultraviolet light are PLA films to, for example, dairy products may require
important parameters in designing the right packaging to additives to block UV light transmission. Effective UV
preserve and protect products until they reach the consumer. stabilizers are able to absorb UV light and thus prevent
The primary wavelengths of interest in packaging applica- damage to light sensitive packaged foods, resulting in
tions are those that fall between 200 and 2 200 nm. This retention of taste and appearance, extension of shelf life and
section of the electromagnetic spectrum can be divided into improvement of product quality. PLA transmits less UV-C
three components: Ultraviolet (UV) band (100–400 nm); light than LDPE (Figure 3), but PET, PS and cellophane
visible spectrum (400–700 nm); near infrared band (700– transmit less UV-B and UV-A than PLA and LDPE. More-
2 200 nm). Ultraviolet radiation accounts for only 3% of the over, PET does not transmit UV-C and UV-B wavelengths,
total radiation that reaches the earth, but it is energetic which are the most damaging for food.
enough to cause chemical reactions, weathering of poly- The visible light band ranges from 400–700 nm. Within
mers, fading of certain dyes and even eye damage. UV light this band, colors range from violet to blue, green, yellow,
is subdivided into three distinct wavelength regions. UV-A orange and red. Each wavelength in the visible light band
(400–315 nm), often referred to as ‘‘blacklight’’, is the causes a particular sensation of color. The eye is not equally
longest wavelength region and lowest in energy. It repres- sensitive to light emitted at all wavelengths. It is most
ents the largest portion of natural UV light and it is sensitive to the light in the yellow and green areas of the
responsible for tanning and pigmentation of the human spectrum. When a light beam strikes a material, some light
skin.[107] UV-B (315–280 nm) is partially blocked by the is transmitted, some reflected and the rest is absorbed. Light
ozone layer and is the most energetic component of natural transmission depends on the reflectance at both surfaces of
UV light. It causes the most photochemical degradation of the material and the absorption of light into the material.
plastics. UV-C (280–100 nm) is generally created from Many different systems are used to characterize visible light
artificial light sources. The UV-C generated by the sun is transmission and color. According to ASTM D1746-03,[109]
totally absorbed by the earth’s atmosphere and never the transparency of plastic sheeting is defined as the trans-
reaches the earth’s surface. The amount of UV light absorp- mission of visible light in the range 540–560 nm. The aver-
tion and transmission is used to characterize polymer age transparency is around 95%. One of the most common
samples. systems used to characterize color is the L*a*b* system,
PLA light barrier properties have been studied and also referred to as the CIELAB system, which is used to
compared with the visible and ultraviolet light transmission determine and to compare sample colors. The CIELAB
rates of standard commercial polystyrene, poly(ethyl- system can be visualized as a cylindrical coordinate system
ene terephthalate), low density polyethylene and cello- in which the axis of the cylinder is the lightness variable L*,
phane films in the range 190–800 nm.[108] Figure 3 shows ranging from 0% to 100% and the radii are the chromaticity
the profiles for PLA and other standard commercial films. variables a* and b*. Variable a* changes from green
PLA shows almost no UV transmission in the lower range (negative) to red (positive) and variable b* changes from
of UV-C (190–220 nm). However, at 225 nm the amount blue (negative) to yellow (positive). Variables L, a and b are
of UV light transmitted by PLA increases significantly. At stated in different norms, ASTM D 6290-98e1[110] and DIN
250 nm, 85% of the UV light is transmitted. At 300 nm, 95% 6176-03.[111] Various standard parameters can be calcu-
of the UV light is transmitted. Thus, while UV-C is not lated from the L*a*b* system variables, such as the color
transmitted, nearly all the UV-B and UV-A light passes difference between two points: DE*ab ¼ [(DL*)2 þ
Table 2. L*a*b* values for PLA (98% L-lactide) and commercial polymer samples.
L* a* b* DE* c) YI
c) a) b) b)
PLA 90.64 0.21 0.99 0.01 0.50 0.04 – 4.67
Cellophane 88.94b) 0.07 0.83b) 0.12 1.45b) 0.03 2.59 6.30
Polystyrene 89.80a) 0.67 0.72b) 0.02 0.49b) 0.05 1.33 4.32
LDPE 89.73b) 0.09 0.92b) 0.01 0.68b) 0.02 0.93 4.67
PET 88.10b) 0.22 1.07b) 0.02 0.08b) 0.03 2.61 5.71
a)
Indicates that the values are not significantly different at the a ¼ 0.05 level (P > 0.01).
b)
Indicates that the values are significantly difference at the a ¼ 0.05 level (P < 0.01).
c)
PLA crystallinity is 40%, and it was provided by Cargill-Dow LLC.
(Da*)2 þ (Db*)2]1/2. In addition, the yellowness index can rotation of poly(D-lactic acid) and poly(L-lactic acid). The
be calculated using the tristimulus values, X and Y; YI ¼ specific optical rotation, [a], of the polymers was measured
100(CxX CzZ)/Y, where Cx ¼ 1.2769 and Cz ¼ 1.0592, in chloroform at a concentration of 1 g dl1 at 25 8C, using
according to ASTM D 6290-98e1.[110] L*a*b* values for a polarimeter at a wavelength of 589 nm. Values of 1568
PLA and other standard commercial polymers are shown in and 156 deg dm1 g1 cm3 were reported for PLLA and
Table 2.a PDLA.
The higher PLA L value is an indicator of a slightly
increased lightness. The negative value of a is indicative of
Infrared
a green tone in the film, and the negative b value indicates
more blue color than cellophane, PS or PET. If we compare Infrared radiation refers broadly to that portion of the
the DE* values, cellophane and PET films are not very electromagnetic spectrum between the visible and the
different from each other, but they are the ones most microwave region (i.e. 2 500–15 000 nm). The infrared
different from PLA. The yellowness index is a number spectrum of commercial PLA was determined by Fourier
calculated from spectrophotometric data that describes the Transform Infrared (FT-IR).[108] For PLA polymers,
change in color of a test sample from clear or white toward maximum absorbance occurs at 240 nm and is attributed
yellow. PLA, PS and LDPE have the same yellowness to the ester group present in the backbone. The principal
index, while cellophane and PET have higher values. The PLA absorption bands in the infrared range are summarized
light yellow color of PLA bottles and trays could create a in Table 4. The strong IR bands at 2 997, 2 946 and
consumer perception that the package is old so the consu- 2 877 cm1 are assigned to the CH stretching region,
mer perception of PLA container color should be nasCH3, nsCH3 and nCH modes. The C O stretching region
determined. is observed as a large band at 1 748 cm1. The region
between 1 500 and 1 360 cm1 is characterized by the
1 456 cm1 CH3 band. The CH deformation and asym-
Refractive Index
metric bands appear at 1 382 cm1 and 1 365 cm1, res-
All polymers have a refractive index that is characteristic of pectively. The bands that appear at 1 315 cm1 and
the polymer structure. The refractive index can be calcu- 1 300 cm1 are due to the CH bending modes. In the region
lated by different theoretical methods based on the molec- of 1 300 cm1 to 1 000 cm1, it is possible to observe the
ular weight and molecular volume of the monomer or C–O stretching modes of the ester groups at 1 225 cm1 and
constitutional unit, the density of the polymer and the the nO–C asymmetric mode at 1 090 cm1. Between
chemical structure of the polymer. The refractive index of 1 000 cm1 and 800 cm1, peaks can be observed at
PLA polymer and of common commercial polymers was 956 cm1 and 921 cm1 which can be attributed to the
calculated by the Lorentz and Lorentz, Gladstone and Dale characteristic vibrations of the helical backbone with CH3
and Vogel methods.[108] Table 3 shows the experimental and rocking modes. Two bands related to the crystalline
calculated refractive indices for PE, PS, PVC, PET and and amorphous phases of PLA were found at 871 cm1
PLA. and 756 cm1. The peak at 871 cm1 can be assigned to the
Light refraction is directly correlated with the isotropy of amorphous phase and the peak at 756 cm1 to the crystal-
the polylactide. Tsuji et al.[113] measured the optical line phase. Similar findings have been reported in the
literature.[57,114,115] Finally, the peaks below 300 cm1
a correspond mainly to CH3 torsion modes and to the skeletal
P-value, also known as the observed or exact level of
significance, or the exact probability of committing a Type I C–C torsions. Infrared spectroscopy data and a more
error. P-value is defined as the lowest significance level at which detailed table of PLA Raman spectroscopy frequencies can
the null hypothesis can be rejected. be found elsewhere.[114,115] Absorption is reported in the
Table 3. Theoretical and experimental refractive index for standard commercial polymers. PLA samples were obtained from Cargill-
Dow LLC.
Polymer n exp. n calculated
Lorentz and Lorentzb) Gladstone and Dalec) Vogeld)
Polyethylene 1.490a) 1.479 1.478 1.469

Polystyrene 1.591a) 1.603 1.600 1.590
Poly(vinyl chloride) 1.539a) 1.544 1.543 1.511
Poly(ethylene terephthalate) 1.63–1.68a) 1.581 1.580 1.560
Poly(98% L-actide) – e) 1.482 1.492 1.500
a)
Values obtained from Van Krevelen.[112]
b)
Values calculated according to Lorentz and Lorentz.[112]
c)
Values calculated according to Gladstone and Dale.[112]
d)
Values calculated according to Vogel.[112]
e)
Experimental value was not obtained.
range of 60 to 2 995 cm1 for both infrared and Raman semicrystalline[35,76] while PLA with 50–93% L-lactic acid
spectroscopy. is strictly amorphous. The presence of both meso- and
D-lactide forms produces imperfections in the crystalline
structure, reducing the percent crystallinity. For amorphous
Physical PLA, the glass transition temperature (Tg) is one of the most
important parameters since dramatic changes in polymer
Physical properties of PLA polymers, as well as other
chain mobility take place at and above Tg. For semicrystal-
polymers, depend on their molecular characteristics as well
line PLA, both the Tg and melting temperature (Tm) are
as ordered structures such as crystalline thickness, crystal-
important physical parameters for predicting PLA behavior.
linity, spherulite size, morphology and degree of chain
The glass transition temperature is also determined by the
orientation. The physical properties of polylactide are rela-
proportion of different lactides. A representative case of
ted to the enantiomeric purity of the lactic acid stereo-
high molecular weight amorphous polylactide is shown in
copolymers. The homopolymers poly(D-lactide) or poly-
Figure 4. Below the b-relaxation temperature, Tb, PLA
(L-lactide) and high D- or L-lactide copolymers have very
polymers are completely brittle. Between Tb and Tg the
regular structures and develop a crystalline phase. High
amorphous polylactide undergoes physical aging and can
molecular weight polylactides are either amorphous or
show brittle or ductile fracture. In the transition between
semicrystalline at room temperature, depending on the
110–150 8C, PLA changes from rubbery to viscous and is
amounts of L, D and meso-lactide in the structure. PLA can
mainly dependent on the molecular weight and the shear
be produced totally amorphous or up to 40% crystalline.
stress. Finally, amorphous PLA decomposes between 215
PLA resins containing more than 93% of L-lactic acid are
and 285 8C. The commercial applications of amorphous
PLA are related to the temperature at which the polylactide
will be used. Amorphous PLA properties depend in part on
Table 4. Infrared spectroscopy data – peak band assignments for how far below Tg the article is used or stored.
PLA (98% L-lactide) infrared spectra. For semicrystalline polylactide, the melting temperature
is a function of the processing conditions and the stereo-
Assignment Peak position
chemistry of the polymer. Figure 5 shows a typical high
cm1 molecular weight semicrystalline PLA. The crystalline
melting temperature, Tm, depends on the presence of meso-
–OH stretch (free) 3 571 lactide in the structure which produces a depression of the
–CH– stretch 2 997 (asym), 2 946 (sym), 2 877 melting temperature as follows: Tm (8C) 175 8C–300 Wm,
–C O carbonyl stretch 1 748
–CH3 bend 1 456 where Wm is the fraction of meso lactide and 175 8C is the
–CH– deformation including 1 382, 1 365 melting temperature of PLA made of 100% L-lactide.[76]
symmetric and asymmetric For semicrystalline PLA, Tg indicates the transition be-
bend tween brittle and ductile fracture. The maximum practically
–C O bend 1 225 obtainable melting point of stereochemically pure polylac-
–C–O– stretch 1 194, 1 130, 1 093
–OH bend 1 047 tide (either L- or D-) is around 180 8C with an enthalpy
–CH3 rocking modes 956, 921 of 40–50 J g1. A reduction in the melting temperature of
–C–C– stretch 926, 868 between 20 and 50 8C can be obtained by the addition of
Figure 4. Metastable states of high molecular weight amorphous polylactides, adapted from Witzke.[76]
D-lactide to the polymer structure. A qualitative and quanti- thermal stability are (1) hydrolysis by trace amounts of
tative understanding of the transition temperatures as well water, catalysed by hydrolysed monomers (lactic acids); (2)
as other polymer properties is important to identify polymer zipper-like depolymerization, catalysed by the remaining
applications. polymerization catalyst; (3) oxidative, random main-chain
According to Ikada and Tsuji,[3] melting temperature scission; (4) intermolecular transesterification to monomer
increases with a rise in molecular weight (M w ) until the and oligomeric esters and (5) intramolecular transester-
maximum practical value. On the other hand, the crystal- ification resulting in the formation of monomer and oligo-
linity of the samples gradually decreases with increasing meric lactides of low M w.
M w . The glass transition temperature is also determined by Table 5 presents the glass transition and melting tem-
the proportion of different lactides present. This results in peratures and the enthalpy of fusion for two PLA, PS and
PLA polymers with a wide range of hardness and stiffness PET films.[108] Test were carried out according to ASTM D
values. The typical PLA glass transition temperature (Tg) 3418–97 and ASTM D 3417–97. Polylactide films undergo
ranges from 50 8C to 80 8C while the melting temperature an endothermic event superimposed on Tg which is ob-
ranges from 130 8C to 180 8C.[3,76] PLA polymer of served during the first differential scanning calorimeter
M n ¼ 430 has a Tg of 8.0 8C and PLA of M n ¼ 22 730 has (DSC) heating. This endothermic relaxation, with an
a Tg of 55.5 8C.[116] The glass transition temperature of average enthalpy of 1.4 J g1 (Table 6), results from a
PLLA is higher than PDLA but this may be partly due to the secondary molecular reordering in the amorphous phase
difference in crystallinity between the two polymers. In of semi-crystalline polymers. The endothermic peak is
general, the glass transition temperature of PLA can be eliminated as the sample is heated above Tg.
represented by a Flory-Fox (Equation (1)) The thermal history of PLLA films strongly affects their
Tg ¼ Tg1 K=M n ð1Þ physical properties since it induces changes in crystallinity
(i.e., long physical aging time affects the ratio of the glassy
where T1 g is the Tg at infinite M w and K is a constant amorphous phase). This phenomenon is clearly observed
representing the excess free volume of the end groups of the as the storage temperature approaches the glass transition
polymer chains. Jamshidi et al.[116] reported that T1 g ¼ temperature of the films. Celli and Scandola[117] found that
58 8C and K ¼ 5.50 104 for low crystallinity PLLA and the decrease in molecular weight of PLLA films increased
that T1 g ¼ 57 8C and K ¼ 7.30 10
4
for amorphous the magnitude of the enthalpy of relaxation at the glass tran-
[117]
PDLLA. Celli and Scandola reported that a decrease sition. Tsuji and Ikada[95] prepared PLLA films which they
in the molecular weight increased the enthalpy of relaxation annealed. They found that PLLA polymer morphology
at the glass transition. Also, they reported that PLLA is strongly depended on the annealing temperature and time
sensitive to thermal degradation. Some reasons for this poor since it alters the spherulite size and morphology. In
Figure 5. Metastable states of high molecular weight semicrystalline polylactide, adapted from
Witzke.[76]
Table 5. Physical properties of PLA (98% L-lactide), PLA (94% atures close to the melting point produced only crystals with
L-lactide), PS and PET.
the highest melting point, longer annealing times produced
PLA(98% PLA(94% PS PET more perfect, higher-melting crystals. This change in
a)
L-lactide)L-lactide)
a)
(atactic)b) crystallization from rapidly forming, lower-melting crys-
tals to more slowly reforming, higher-melting crystals
Tg 71.4 66.1 100 80 occurred gradually as the annealing temperature progressed
8C from 100 8C to 140 8C. Samples less than 300 000 g mol1
Relaxation enthalpy 1.4 2.9 N/A N/A developed 30–50% crystallinity. Poly(lactic acid) is a
Jg 1 slowly-crystallizing material, similar to poly(ethylene
Tm 163.4 140.8 N/A 245 terephthalate). More details on the crystallization kinetics
of poly(lactic acid) and copolymers can be found else-
8C
Enthalpy of Fusion 37.5 21.9 N/A 47.7 where.[31,33–36,57,77,89,91,93,94,116,125,126,129–133] Nucleation
1
parameters for poly(L-lactic acid) crystallization in iso-
Jg thermal and non-isothermal conditions were determined
Percent Crystallinity 40 25 N/A 38
using differential scanning calorimetry and electron micro-
a)
PLA samples were provided by Cargill Dow LLC. scopy. Equation (2) shows the nucleation parame-
b)
PS used in packaging is atactic, so it does not crystallize. Since it ters[89,93,130,132]
is an amorphous polymer, it does not have a defined melting
4bsse Tm
point, but gradually softens through a wide range of temper- Kg ¼ ð2Þ
atures. DHf k
where Kg is the nucleation constant, s the lateral surface

addition, annealing effects depend on pretreatments such as energy, se the fold surface energy, b the layer thickness of
melting before annealing. Annealing studies of poly- the crystal, DHf the heat of fusion/unit volume and k the
(L-lactic acid) at 448 K show an increase in melting temper- Boltzman constant. Table 6 shows the nucleation para-
ature and heat of fusion with annealing time, suggesting an meters from isothermal and non-isothermal kinetic analysis
increase in lamellar thickness. of PLLA.
Solving Equation (2), Tm ¼ 480 K (207 8C), Tg ¼ 328 K
Crystallinity (55 8C), DHf ¼ 11.11 108 erg cm3 or 111.083 106 J
m2, b ¼ 5.17 108 cm and se ¼ 60.89 erg cm2 or
The crystallization kinetics of polylactides have been 6.089 104 J m2. The peak crystallization temperature
extensively studied.[35–38,54,73,76,77,79–81,85,89,91,118–126] In- obtained was 125 8C. In addition, Urbanovici et al.[129]
vestigation of poly(L-lactide-co-meso-lactide) in the range obtained isothermal DSC crystallization data for poly(lactic
of 0% to 9% meso-lactide showed that the crystallization acid) at six temperatures between 90 and 130 8C. They used
kinetics are strongly dependent on the copolymer composi- the Avrami equation which presents the degree of crystal-
tion.[94] Tsuji and Ikada[122] reported that PLLA can crystallization as a function of time and temperature.
lize in the presence of D-lactide. However, as the structure
becomes more disordered, the size of the spherulites and the
time for crystallization increases. Density
PLLA exhibits strong piezoelectricity when the polymer The density of amorphous poly(L-lactic acid) has been
chains are highly oriented.[3,100] Molecular orientation reported as 1.248 g ml1 and for crystalline PLLA as
increases the mechanical strength of PLLA plastics. If 1.290 g ml1.[76] The liquid density of L-lactide, meso-
orientation is performed at low temperature, the resulting lactide and amorphous polylactide can be expressed using
PLLA has enhanced strength without a significant increase
in crystallinity. Ou and Cakmak[127] reported that simulta-
neous biaxial stretching produced PLA films with different Table 6. Nucleation Parameters from isothermal and non-
crystalline order and orientation levels, which may have a isothermal kinetic analysis for PLLA, adapted from
Vasanthakumari and A. J. Pennings,[93] Kishore[130] and
significant impact on the final properties of the films. Vasanthakumari.[132]
Crystallization of the amorphous, but thermally crystal-
lizable, PLA copolymers (various L- to D-contents) can be Parameter Isothermal Non-isothermal
initiated by annealing at temperatures between 75 8C and 5
the melting point. Annealing crystallizable PLA copoly- Nucleation parameter, kg 10 2.44 2.69
sse 106 753 830
mers to induce crystallinity often produces two melting
peaks. Yasuniwa et al.[128] found a double melting point in J2 m4
PLLA polymers and attributed them to slow rates of Lateral surface energy, s 103 12.0 13.6
2
crystallization and recrystallization. Annealing at temper- Jm
Equation (3). (N m1) or in erg cm2 (dyn cm1). The surface energy
r150 C of polymers can be modified by flame treatment, corona
rðg=cm3 Þ ¼ ð3Þ discharge treatment and ozone treatment, all of which
1 þ al ðTð CÞ 150Þ
impart some oxidation to the surface of the polymer and
where al ¼ 7.4 104 8C1 0.17 104 8C1 and is the promote adhesion in printing and converting operations. In
liquid thermal coefficient of expansion obtained by non– general for films, corona treatment is chosen to increase
linear regression. surface tension. In this process, high-voltage electric energy
The density of solid polylactide was reported as is discharged on the surface of the film, which increases the
1.36 g cm3 for L-lactide, 1.33 g cm3 for meso-lactide, surface energy. ‘‘In general, the ability of a substrate to
1.36 g cm3 for crystalline polylactide and 1.25 g cm3 anchor inks, coatings or adhesives is directly related to its
for amorphous polylactide. The density of the pure crystals surface energy. If the substrate surface energy does not
can be determined by using Equation (4). significantly exceed the surface tension of the fluid which is
wc to cover it, wetting will be impeded, and a poor bond will
rc ðg=cm3 Þ ¼ ð4Þ result.’’[134] The surface energies of two polylactide films,
1=r ð1 wc Þ=ra
poly(98% L-lactide) and poly(94% L-lactide), were meas-
where rc is the density of the pure crystal, r is the density of ured by ACCU DYNE TEST marker pens from Diversified
semi-crystalline polylactide, wc is the crystalline fraction Enterprises, Claremont, NH according to ASTM D 2578-
and ra is the density of the amorphous polylactide, so the 94[134] and are shown in Table 7, with the surface energies of
ratio of purely crystalline and amorphous polylactide other standard polymers.
(rc/ra) is 1.088.
The densities of two polylactides, poly(98% L-lactide) Moisture Sorption Isotherm
and poly(94% L-lactide), were measured by the level to
Moisture sorption isotherms were determined for two poly-
which the PLA specimen sinks in a liquid column.[108]
lactide films, poly(98% L-lactide) and poly(94% L-lactide) in
Poly(98% L-lactide) had a density of 1.240 0.002 g cc1
therangeofAw ¼ 0to0.9andat5,23and40 8C,whereAw isthe
and poly(94% L-lactide) had a density of 1.243
ratio of the partial pressure of water to the saturation (vapor)
0.002 g cc1.
pressure of water at a specified temperature.[108] PLA films
stored for more than one week at 5, 23, and 40 8C and Aw
Friction Coefficient
between 0.11 and 0.94 did not absorb measurable amounts of
Friction is a complex summation of different factors such as water. Previous work with PLA pellets (M n ¼ 50 000–
internal friction and surface shear friction and it is measured 100 000 Daltons) indicated very low levels of water absorp-
in terms of the friction coefficient. Internal friction is tion (i.e. 8 000 ppm at 25 8C and Aw ¼ 0.9, with an equilibrium
important in cyclic processes like rolling friction. Surface time no greater than 72 h).[76] Witzke[76] also reported that
friction is the interaction that takes place at the surface. water absorption was fairly insensitive to moderate tempera-
Even the smoothest surfaces are rough on a sub-micro- ture changes. PLA is moderately polar with a solubility
scopic scale. The friction coefficient plays a very important parameter (d) of 19–20.5 MPa0.5.[1] The solubility parameter
role in film passing over free-running rolls, bag forming and of water is 48 MPa0.5. When the difference between the
the wrapping of film around a product. The upper limits of solubility parameter of water and a polymer increases,
the static friction coefficients for two polylactide films, the water sorption decreases. For PET the d is 16 MPa0.5
poly(98% L-lactide) and poly(94% L-lactide), were deter- and the water absorption 60 ppm at 25 8C, with an Aw ¼ 0.5.
mined by an inclined plane method.[108] Poly(98%
L-lactide) had a friction coefficient equal to ms ¼ 0.371
Table 7. Experimental and calculated surface tension in
0.011, and poly(94% L-lactide) equal to ms ¼ 0.319 0.011. dyn cm1 for PLA, PET, PP, PE and PS.
The difference is due to different surface treatments.
Typical friction coefficients of PS and PET films are Polymer gs experimental gs calculated
ms ¼ 0.4 and ms ¼ 0.35, respectively.[112]
dyn cm1 dyn cm1
Surface Energy Poly(98% L-lactide)a) 42 45b)

Polyethylene 35.7c) 31.5b)
Surface energy is critically important to many converting Polypropylene 29.6c) 32.5b)
operations and is a direct manifestation of intermolecular Poly(ethylene terephthalate) 44.6c) 49b)
tension. Molecules at the surface of the polymer are not Polystyrene 40.7c) 43b)
surrounded by other molecules, so the molecular forces are a)
PLA samples were obtained from Cargill Dow LLC.
unbalanced and the molecules have additional energy b)
Calculated from gs ¼ (Ps/V)4, where Ps is the parachor in
compared with the molecules inside the liquid or solid. (cm3 mol1) (erg cm2)1/4 and V is the molar volume.
The surface or interfacial tension is expressed in J m2 c)
Experimental values obtained from Van Krevelen.[112]
For PS (d ¼ 19 MPa0.5) the water absorption was 320 ppm at poly(94% L-lactide). In addition, the change in the enthalpy
25 8C and Aw ¼ 0.5.[76] In PLA films water absorption is of fusion as function of time, temperature and humidity was
difficult to measure below 100 ppm.[108] One reason could evaluated. For poly(98% L-lactide), no statistically sig-
be that the chemical composition of the PLA films used by nificant change in the enthalpy of fusion as a function of
Auras[108] and the chemical composition of the pellets used time, temperature and humidity was found (Pvalue > 0.05).
by Witzke[76] was different (i.e. they contained different For poly(94% L-lactide), however, the change was statisti-
amounts of L- and D-lactide isomers). Another possibility is cally significant (Pvalue < 0.05). One reason for the change
that the porous structure of the pellets trapped water. in the enthalpy was likely to be the low molecular weight
sealant layer.
Variation of the Glass Transition and Melting
Heat Sealing Properties
Temperature with Time, Temperature and Humidity
Working with amorphous PLA sealant films, Gruber and
In polymers that absorb very low amounts of water, such as
O’Brien[17] reported sealing temperatures of 80 and 85 8C
PLA and PET, the effect of water on the physical properties
and an ultimate tensile strength of 360 g cm1 over a broad
can be crucial to the polymer’s general performance. For
temperature range. They also reported a peak hot tack
example, in the case of PET, water plasticizes the amor-
strength of 450 g cm1 in a PLA made by coextrusion.
phous phase, which leads to a decrease of the Tg from about
Auras[108] determined the best sealing conditions for
80 8C in a dry state to about 57 8C in a saturated state and a
poly(94% L-lactide) films. Figure 7 shows the peel force as a
consequent reduction of the elastic modulus.[135] Besides
function of the sealing temperature. The type of failure and
the changes in the physical and mechanical properties,
the amount of shrink that the film exhibits when sealed at
surprising changes in polymer barrier properties can occur
each temperature is also shown. Poly(94% L-lactide) had a
as a result of the presence of relatively small quantities of
constant peel force until the sealing temperature exceeds
absorbed water. Therefore, changes in the physical proper-
115 8C. At 120 8C the peeling force increased by 25%,
ties (i.e. Tg, Tm and enthalpy of fusion) as a function of the
though the material failed before seal failure. The maxi-
storage time at different temperatures and water activities
mum and minimum peel forces did not differ much from the
can be used as an indicator of the change in the performance
average values, which indicates uniform sealing of the PLA
of the polymers under different environmental conditions.
samples. When the heating temperatures exceeded 110 8C,
Variation in the glass transition and melting temperature
the shrinkage of the sample increased to 10% and then 20%
with time, temperature and humidity for two polylactide
at a temperature of 120 8C. The best sealing condition for
films of rectangular shape (5 cm 1 cm 25.4 mm),
poly(94% L-lactide) was a temperature of around 110 8C for
poly(98% L-lactide) and poly(94% L-lactide), stored for
one to five seconds. The strongest peel seal can be achieved
120 d at 5, 23 and 40 8C, and 0.11, 0.53 and 0.94 water
at temperatures near the melting point of the inner sealant
activities has been reported.[108] The glass transition and
layer of the polymer film. Sealing at a temperature above the
melting temperatures were monitored every week for the
fusion temperature resulted in a weld seal and a high
first month and after that every 30 d. Figure 6a, b and c show
shrinkage percentage. The dwell time for sealing did not
the change in the glass transition temperature for poly(98%
result in any considerable difference in seal strength once
L-lactide) as a function of time at 5, 23 and 40 8C with Aw of
the temperature at the interface reached the set temperature.
0.11, 0.52 and 0.94. For poly(98% L-lactide), the variation
Sufficient pressure is required to bring the sealing surfaces
in Tg was statistically significant as a function of time
together at the sealing temperature. Once achieved, how-
(Pvalue < 0.05). The major reduction in Tg as a function of
ever, a higher pressure did not add to the seal strength. The
time was reached prior to seven days. After this no
combination of the delamination failure mode shown in
statistically significant change was recorded (Pvalue ¼
PLA with this peel strength value may indicate the potential
0.084). No statistically significant change of Tg as function
for PLA to be incorporated into an ‘‘easy-open’’ package.
of storage temperature was found (Pvalue ¼ 0.692). Humid-
ity had an effect on Tg, at Pvalue ¼ 0.05. Figure 6d, e and f
Heat Deflection Temperature
show the change in the glass transition temperature for
poly(94% L-lactide) as a function of time at 5, 23 and 40 8C Poly(98% L-lactide) lost 50% of its modulus and storage
with Aw of 0.11, 0.52 and 0.94. The reduction of Tg as a modulus at 80 8C and 87% of the storage modulus at 100 8C.
function of time was statistically significant after seven days Figure 8 shows DMA curves for poly(98% L-lactide). The
(Pvalue ¼ 0.002). The change in Tg as a function of storage use of poly(98% L-lactide) at a temperature higher than the
temperature and the change of Tg with humidity were not sta- glass transition resulted in an almost complete loss of
tistically significant (Pvalue ¼ 0.124 and 0.069, respectively). the film strength. For poly(94% L-lactide), 50% of the stor-
Melting temperature was analyzed in the same way as the age modulus was lost at 82 8C and a total loss of the storage
glass transition temperature and no significant changes modulus was found at 90 8C (not shown). The increased loss
were found (Pvalue > 0.05) for poly(98% L-lactide) and rate of the biaxially oriented poly(94% L-lactide) film is
Figure 6. a, b, c represent the variation in the glass transition as a function of time for poly(98%
L-lactide) storage at 5, 23, and 40 8C with Aw of 0.11, 0.52 and 0.94, and d, e, f represent the variation in
the glass transition variation as a function of time for glass transition variation for poly(94% L-lactide)
storage at 5, 23, and 40 8C with Aw of 0.11, 0.52 and 0.94.
attributed to a lower percent crystallinity (wc ¼ 25%) than blowing, sheet forming, fiber spinning and thermoforming.
the poly(98% L-lactide) (wc ¼ 40%) and a lower melting Polylactide melt behavior is similar to polystyrene. Melt
temperature. viscosities of high molecular weight PLA were reported as
5 000 to 10 000 poise (500–1 000 Pas) at 10 to 50 s1.[57]
Rheological
The weight average molecular weight of PLA used for
The shear viscosity of PLA polymers affects thermal injection molding is around 100 000 Daltons and approxi-
processing, such as injection molding, extrusion, film mately 300 000 for cast-extruded film grades. The amount
Figure 8. DMA curves of poly(98% L-lactide) (wc ¼ 40%)

showing E0 , E00 and tan d as a function of temperature at a
Figure 7. Peel force and shrink percentage as a function of frequency of 1 Hz.
sealing temperature.
of plasticizer plays an important role in the melt viscosity. non-Newtonian fluid with behavior adequately described
The PLA working temperature is dependent on its melt using a power law equation.[143] On the other hand, Dorgan
viscosity, which depends on the weight-average molecular et al.[144] working with PLAs with a wide range of optical
weight, the L/D ratio, the amount of plasticizer, the shear compositions found that the melt properties were not
rate, the type of melt processing and the amount of energy dependent on the optical composition of the polymers.
put into the polymer.[136] A number of dilute-solution Witze investigated the linear viscoelastic properties and the
experiments have been performed with polylactide, the data lactide-polylactide mixture viscosities occurring during
from which have been used to create a number of Mark- polymerization for different polylactide polymers with dif-
Houwink equations. The Mark-Houwink equation repres- ferent monomeric compositions (L-, meso-, D-lactide)
ents the relationship between Z, the intrinsic viscosity, and between 68 and 151 8C.[76] He concluded that the zero-
the molecular number or weight and is a function of the type shear viscosity of amorphous polylactide depended on its
of polylactide, the solvent used and the temperature of the isomeric makeup, weight average molecular weight and
solution. Table 8 shows the Mark-Houwink constants for the temperature, between Tg and Tg þ 100 8C.[76] Cooper-
various polylactide polymers. White and Mackay[145] reported that PLLA melts have a
Semicrystalline PLA has a higher shear viscosity than critical molecular weight for entanglement of 16 000 g
amorphous PLA. However, as the temperature increases, mol1 and an entanglement density of 0.16 mmol cm3 at
the shear viscosity decreases for both amorphous and 25 8C. In addition, the terminal viscosity (Zo) was found to
semicrystalline PLA.[143] The PLA melt is a pseudoplastic, be dependent on chain length to the fourth power. For
Table 8. Mark-Houwink constants for poly(lactic acid) in selected solvents (K ¼ dl g1), adapted from Garlotta,[57] Schindler[136] and
Sinclair.[137] PDLLA provided by Cargill-Dow LLC is insoluble in ethyl acetate.
Poly(lactic acid) Mark-Houwink constant Solvent
PLLA [Z] ¼ 5.45 104 Mv0.73 25 8C in chloroform[33,97]

PDLLA [Z] ¼ 2.21 104 Mv0.77 25 8C in chloroform[33,97]
PDLLA [Z] ¼ 1.29 105 Mv0.82 25 8C in chloroform[138]
Linear PLLA [Z] ¼ 4.41 104 Mv0.72 25 8C in chloroform[139]
‘‘Star’’ PLLA (6 arms) [Z] ¼ 2.04 104 Mv0.77 25 8C in chloroform[139]
PDLLA [Z] ¼ 2.59 104 Mv0.689 35 8C in THF[140]
PDLLA [Z] ¼ 5.50 104 Mv0.639 31.15 8C in THF[140]
PLLA (amorphous) [Z] ¼ 6.40 104 Mv0.68 30 8C in THF[87]
PLLA (amor./semicryst.) [Z] ¼ 8.50 104 Mv0.66 30 8C in THF[87]
PLLA (semicryst.) [Z] ¼ 1.00 103 Mv0.65 30 8C in THF[87]
PDLLA [Z] ¼ 2.27 104 Mv0.75 (one point method) 30 8C in benzene[141] Tuan-Fuoss viscometer
PDLLA [Z] ¼ 6.06 104 Mv0.64 25 8C in chloroform[136]
PLLA [Z] ¼ 5.72 104 Mv0.72 25 8C in chloroform[136]
PDLLA [Z] ¼ 1.58 104 Mv0.78 25 8C in ethyl acetate[142]
PDLLA [Z] ¼ 1.63 104 Mv0.73 25 8C in ethyl acetate[142]
branched PLLA, the entanglement happens at a molecular heating ramp of 10 8C min1 and purged with nitrogen at
weight about four-fold that of linear PLLA and the terminal 50 ml min1. Zero-order kinetics are followed between
viscosity (Zo) was dependent on chain length to the 4.6 40 and 80% volatilization, which are consistent with a
power.[146] depolymerization phenomenon. Further details of this
The melt flow index is indicative of the extrudability of process can be found elsewhere.[76] Thermal decomposition
thermoplastic materials. Values of 8.51 0.19 g/10 min is independent of initial lactide isomer distribution. The
and 7.83 0.15 for poly(98% L-lactide) and poly(94% activation energy for PLA weight loss is 139 kJ mol1
L-lactide), respectively, were found at 200 8C and 5 kg of between 186 8C and 257 8C. Polylactide has a similar
weight.[108] thermal stability to PVC but is considerably less stable than
PS, PP, PE and PET.
Processing
PLA can be processed by injection molding, sheet Mechanical
extrusion, blow molding, thermoforming and film forming.
The mechanical properties of poly(lactic acid or lactide)
Cargill Dow LLC commercialized PLA polymer under the
have been studied by many investigators.[11,17,18,22,32,33,39,57]
name of Natureworks for extrusion, thermoforming, cast
Results for polylactides produced and processed under
film, blown film and injection stretch blow molded bottles
different conditions are shown in Table 9.
and containers.[17,147] Mitsubishi Plastics in Japan also com-
The variation shown in Table 10 is due to the degree of
mercialized PLA polymers for different applications under
orientation in the samples and the stereochemical composi-
the brand name of LACEA.[18]
tion of various poly(lactic acid) samples. Annealing L-PLA
Hartmann[49] reported that the molecular weight for
increased the tensile strength due to the increase in the
polymers used in extrusion and injection molding is usually
stereoregularity of the chain and increased the impact
reduced over the virgin material. PLA quickly loses its
resistance due to the crosslinking effects on the crystalline
thermal stability when heated above its melting point.
domains.[57,151]
Significant molecular weight degradation occurred when
In general, the modulus and tensile strength were greatest
PLAwas held 10 8C above its melting point for a substantial
for PLA polymers with a viscosity-average molecular
period of time.[49,57] Migliaresi et al.[148] measured the
weight above 55 000 g mol1.[49,57] The impact strength
reduction in molecular weight due to thermal degradation
and the Vicat softening temperature increased with molec-
and attributed it to chain splitting and not to hydrolysis as
ular weight and crystallinity.[49,57]
had been previously reported. They did not observe
Perego et al.[33] who worked with PLLA having molec-
oxidation of PLA. The degradation of PLA is not only a
ular weights of 35 000 and 55 000 Daltons found an increase
consequence of the thermal degradation of the PLA, but the
of almost 20% in the modulus of elasticity for poly(L-
amount of residual monomer in the resin also has an impor-
lactide) compared with poly(D,L-lactide). In addition, they
tant effect in inducing early degradation of the polymer.
demonstrated that the impact resistance was strongly
PLLA polymers have a narrow processing window
influenced by crystallinity.[33]
(12 8C) although a 90/10 L- to D-copolymer has a much
The tensile strength and the elastic modulus values for
wider window of processing conditions (40 8C) due to its
poly(98% L-lactide and 94% L-lactide), PS and PET were
lower melting temperature.[57] PLA can be plasticized with
measured and are presented in Table 10. The higher content
lactides, oligomeric lactic acid and a wide variety of
of L-lactide in the films contributes to a higher tensile
conventional plasticizers. In general, PLA plasticizing
strength. Although poly(98% L-lactide) has greater elonga-
agents are low molecular weight lactide and glycol acids.
tion at yield than poly(94% L-lactide), the latter has an
However, Bechtold et al.[149] found that a copolymer made
elongation at break 7 times greater than poly(98%
from lactic acid and ethylene oxide could be used as a
L-lactide), which indicates that poly(94% L-lactide) is more
macromolecular plasticizing agent for commercial PLA.
plastic. The tensile strength values obtained for both poly-
Other biocompatible plasticizers such as glycerol, citrate
lactides are within the range of values reported in the
ester, polyethylene glycol, PEG monolaurate and oligo-
literature for PS under the same testing conditions. How-
meric lactic acid have also been used to improve the brittle
ever, when compared to PET, both PLA films had lower
behavior of PLA.[150] Glycerol is the least efficient of these
values. The impact resistance of poly(98% L-lactide) films
plasticizing agents, and polyethylene glycol is the most
is around 360 g.
efficient. A reduction in the glass transition temperature from
58 8C to 12 8C was found when plasticizers were used.[150]
No reduction in the melt temperature was observed.
Solubility
PLA polymers start to thermally degrade at 300 8C and
completely decompose at 400 8C when tested under dried According to Kharas et al.[46] polylactides are soluble in
conditions by thermal gravimetrical analysis (TGA) with a dioxane, acetonitrile, chloroform, methylene chloride,
Table 9. Mechanical properties of poly(L-lactide), adapted from Table 11. Solubility parameters for polylactides, adapted from
Perego et al.[33] and Garlotta.[57] The specimens were obtained by Garlotta.[57]
injection molding at a temperature of 195 8C.
Determination method Solubility parameter
L-PLA Annealed L-PLA D,L-PLA
(Mv ¼ 66 000)a) (Mv ¼ 66 000) (Mv ¼ 114 000) cal0.5 cm1.5
Tensile strength 59 66 44 Density in solution[152] 10.25 0.16

Density in solution[153] 10.29 0.13
MPa Limiting viscosity number, [Z][152] 10.00 0.20
Elongation 7.0 4.0 5.4 Limiting viscosity number, [Z][153] 10.00 0.23
at break Group Contribution Methods
% Small[154] 9.7
Modulus of 3 750 4 150 3 900 Hoy[154] 9.9
Van Krevelen[154] 9.4
elasticity
Fedors[154] 11.1
MPa
Yield strength 70 70 53
ethyl acetate or tetrahydrofuran. All polylactides are
MPa
Flexural strength 106 119 88 insoluble in water, some alcohols and alkanes. Solubility
parameters were measured and reported to be around
MPa 10.3 cal1/2 cm1.5 for amorphous poly(D,L-lactide). Solubi-
Unnotched 195 350 150
izod impact lity parameters from the literature are reported in Table 11.[57]
Tsuji and Sumida[1] found that lactides in phosphate, acid
J m1 and alkaline solutions had solubility parameter (ds) values of
Notched 26 66 18 4.0–6.2 cal0.5 cm1.5.
izod impact
The relative affinity of a polymer and a solvent can be
J m1 assessed using solubility parameters. Auras[108] estimated
Rockwell 88 88 76 the affinity between a number of different solvents (alkenes,
hardness
Heat deflection 55 61 50 aromatic hydrocarbons, halohydrocarbons, ethers, ketones,
temperature aldehydes, esters, nitrogen compounds, sulfur compounds,
acid halides and anhydrides, alcohols, acids, phenols and
8C polyhydric alcohols) and polylactide, as well as PET and
Vicat 59 165 52
penetration PS. The Hansen[153] extension of the Hildebrand (1916)
enthalpy of mixing between a solvent and a polymer was
C used to determined the interaction between PLA and the
a) different solvents. Figure 9 and 10 show two-dimensional
Mv is the molecular weight.
plots of the affinity between nitrogen compounds, alcohols
and polylactide, as well as poly(ethylene terephthalate)
1,1,2-trichloroethane and dichloroacetic acid. Ethyl ben- (PET) and polystyrene (PS). A detailed study of other
zene, toluene, acetone and tetrahydrofuran only partly solvent interactions with PLA can be found elsewhere.[108]
dissolve polylactides when cold, though they are readily The solubility regions of PLA, PET and PS can be
soluble in these solvents when heated to boiling temper- approximated by a circle with a radius of about 2.5 d units
atures. Crystalline poly(L-lactide) is not soluble in acetone, with centers at dv ¼ 19.01; dh ¼ 10.01 for PLA, dv ¼ 19.77;
Table 10. Mechanical properties of poly(98% L-lactide), poly(94% L-lactide), PS and PET films.[108]
Poly(98% L-lactide)a) Poly(94% L-lactide)a) PS Biaxial PET
MD CD MD CD
Tensile yield stress 72 65 84 74 55–82 275

MPa (kpsi) (10.5) (9.5) (12.2) (10.7) (8–12) (40)
Percent elongation at yield 5 4 3 4 – 6
Percent elongation at break 11 5 78 97 3–40 60–165
Elastic modulus 2.11 2.54 2.31 2.87 3.2 2.8–4.1
GPa (kpsi) (306.4) (368.3) (335.4) (416.3) (464) (400–600)
a)
PLA samples were provided by Cargill Dow LLC.
Figure 10. Volume dependent cohesion parameter (dv) versus

Hansen hydrogen bonding parameter for polylactide and alcohol.
Values indicated for solvents with Dd < 5 MPa1/2 (3CP, 3-
chloropropanol; BEA, benzyl alcohol; CHL, cyclohexanol; 1PL,
1-pentanol; 2EB, 2-ethyl-1-butanol; DAL, diacetone alcohol;
DBU, 1,3-dimethyl-1-butanol; ELA, ethyl lactate; BLA, butyl
Figure 9. Volume dependent cohesion parameter (dv) versus
lactate; EME, ethylene glycol monoethyl ether; DGM, diethylene
Hansen hydrogen bonding parameter for polylactide and nitrogen
glycol monoethyl ether, methyl; DGE, diethylene glycol mono-
compounds. Values indicated for solvents with Dd < 5 MPa1/2
ethyl ether, EGB, ethylene glycol mono-butyl ether; 2EH, 2-ethyl-
(PPN, propionitrile; BTN, butyronitrile; 1DH, 1,1,-dimethylhy-
1-hexanol; IOL, 1-octanol; 2OL, 2-octanol; DGN, diethylene
drazine; PYR, pyridine; PPL, propylamine; MPL, morpholine;
glycol mono-butyl ether; 1DE, 1-decanol; TDA, 1-tridecanol;
ANI, aniline; M2P, N-methyl-2-pyrrolidone; BTL, butylamine;
NON, nonyl; OA9, oleyl alcohol).
CHL, cyclohexylamine; DFM, N,N-dimethylformamide; DTA,
N,N-dimethylacetamide; TMU, tetramethylurea).
dh ¼ 10.97 for PET and dv ¼ 15.90; dh ¼ 5.00 for PS and poly(98% L-lactide) film had a higher CO2 permeability
are the corresponding solubility parameters.[108,152,155] coefficient than poly(94% L-lactide). The permeation
The solvents inside the circle show interaction with PLA activation energy was lower for poly(98% L-lactide) resin.
and the other polymers. Note that the distortions from The CO2 permeability coefficients for PLA resins are
perfect circles are due to the differing scales used for the y lower than the reported value for crystalline PS at 25 8C and
and x axes. 0% RH (1.55 1016 kg m/m2 s Pa),[156] but higher than
that for PET (1.73 and 3.17 1018 kg m/m2 s Pa at 0%
RH at 25 8C and 45 8C, respectively).
Barrier
Carbon Dioxide Oxygen
PLA carbon dioxide barrier properties have been measured Lehermeier[5] reported an oxygen permeation coefficient
by different investigators. Carbon dioxide permeation of for PLA of 3.3 1017 kg m/m2 s Pa and an activation
1.76 1017 kg m/m2 s Pa with an activation energy of energy of 11.1 kJ mol1. Auras[157] determined and com-
6.1 kJ mol1 was reported by Lehermeier.[5] Auras[108] pared the diffusion, solubility and permeability coefficients
determined the carbon dioxide barrier properties of two (D, S, P) of PET and two PLA films by using an isostatic
PLA films. Table 12 presents CO2 permeability coefficient technique at 1 and 0.21 atmosphere pressure at three
values as a function of temperature in the range 25–45 8C at temperatures (5, 23 and 40 8C) and four water activities (0,
0% RH. The activation energy was calculated according 0.3, 0.6 and 0.9). Figure 11 shows the oxygen permeability
to the Arrhenius equation. In the range of 25 8C to 45 8C, coefficient for poly(98% L-lactide) film as a function of the
Table 12. CO2 permeability coefficients and activation energy for PLA resins.a)
Resin P 1017 Ep
2
kg m/m s Pa kJ mol1
Temperature
8C
25 30 35 40 45
Poly(98% L-lactide) 2.77 0.05 3.12 0.05 3.42 0.06 3.78 0.06 4.18 0.15 15.65 0.63
Poly(94% L-lactide) 1.99 0.06 2.29 0.06 2.52 0.06 2.87 0.04 3.35 0.06 19.44 0.90
a)
PLA samples were provided by Cargill Dow LLC. Poly(98% L-lactide) has 40% crystallinity and Poly(94% L-lactide) has 25%
crystallinity.
water activity. A significant increase in the oxygen Poly(98% L-lactide) has higher crystallinity than
permeability coefficient was observed as temperature poly(94% L-lactide), which generates a more tortuous path
increased. PLA shows an increase in the oxygen perme- for the permeation of oxygen molecules. Since the crystal-
ability coefficient from 3.5 1018 kg m/m2 s lization of polymers tends to decrease the amorphous
Pa at 5 8C to 11 1018 kg m/m2 s Pa at 40 8C in the volume available for diffusion, the diffusion coefficient and
absence of moisture. At higher water activity levels the solubility of more amorphous polymers are higher than
(Aw ¼ 0.9), the oxygen permeability coefficient decreases those of glassy crystalline polymers. PET and PLA are both
slightly to 8.5 1018 kg m/m2 s Pa at 40 8C. Reduction hydrophobic films that absorb very low amounts of water
in the oxygen permeability coefficient as water activity and show similar barrier property behavior.
increases (at a constant temperature) is shown in Figure 11
for the three temperatures tested. This reduction is most
Water
pronounced at 40 8C.
The difference between the values obtained by Auras[157] Water vapor permeability coefficient (WVPC) values were
and the values from Lehermeier[5] can be explained by determined at 10, 20, 30 and 37.8 8C in the range of 40% to
differences in the crystallinity and processing conditions 90% RH.[108,158] Figure 12 shows that, surprisingly, the
used to produce the films. permeability for 98% L-lactide polymers is practically
The enthalpy of sorption, DHS, the activation energy of constant over the range studied, despite PLA being a polar
diffusion, ED, the apparent activation energy of permeation, polymer.
EP, and the values of P0, S0 and D0 are presented in Table 13. WVPC of PET films showed no significant change as a
Further details can be found elsewhere.[157] function of relative humidity. The average WVPC for PET
was 1.1 0.1 1015 kg m/m2 s Pa at 25 8C in the 40%
to 90% RH range. The reported WVPC of PS is 6.7
1015 kg m/m2 s Pa at 25 8C.[156] The activation energy
for the water vapor permeation process is EP ¼ 9.8 kJ
mol1 for 98% L-lactide and EP ¼ 10.1 kJ mol1 for 94%
L-lactide. Both activation energies are negative.
Water vapor permeation was also measured in some
NatureWorksTM PLA polymers from Cargill Dow LLC.[29]
A water vapor transmission rate of 340 g mL/(m2 day)
was reported, but the conditions under which this test was
performed are not clear. Shogren[159] measured the water
vapor transmission rate of crystalline and amorphous PLLA
and reported an activation energy of 5 kJ mol1 for
amorphous PLLA and a negative activation energy of
0.1 kJ mol1 for crystalline PLLA. Siparsky et al.[160]
reported a permeability coefficient of 9.63 1014 kg m/
m2 s Pa, a solubility coefficient of 4 104 m3/m3 Pa
Figure 11. Oxygen permeability coefficient as a function of and a diffusion coefficient of 4 1012 m2 s1 at 20 8C and
water activity for poly(98% L-lactide). a water activity of Aw ¼ 0.5 in PLA films. They reported an
Table 13. Pre-exponential terms, enthalpy of sorption, activation energy for diffusion and permeation in the oxygen mass transport
through PET and PLA films at different water activity conditions.
Material Water Activity P0 1014 EP D0 1012 ED S0 103 DHS
kg m/m2 s Pa kJ mol1 m2 s1 kJ mol1 kg/m3 Pa kJ mol1
PET 0.0 6.2 30.3 6.6 11.8 9.6 18.5

0.3 3.0 28.6 2.9 9.5 10.2 19.1
0.6 4.7 29.9 10.1 11.6 4.6 18.3
0.9 2.4 28.4 38.9 14.2 0.6 14.1
Poly(98% L-lactide) 0.0 9.0 23.6 300 1.0 2 667 22.6
0.3 12.4 24.4 981 3.2 1 264 21.2
0.6 4.9 22.2 34.2 5.0 141 17.2
0.9 2.0 20.2 27.8 3.3 72.0 16.9
Poly(94% L-lactide) 0.0 3.0 21.1 0.0004 12.1 N/Aa) N/A
0.3 0.9 18.7 14.9 12.5 N/A N/A
0.6 3.1 21.6 0.9 5.0 N/A N/A
0.9 2.0 20.6 17 202 28.0 N/A N/A
a)
N/A: not applicable.
enthalpy of sorption of 40 kJ mol1 and activation energy diffuse in cluster form. On the other hand, some researchers
of diffusion of 49 kJ mol1. Yoon et al.[161] found approxi- have shown that clusters of water are not present in the
mately the same enthalpy of sorption (48.4 kJ mol1) polymer matrix.[76,163,164] The water permeation model in
when working with semicrystalline PLA. PLA is not yet completely understood.
Water sorption and diffusion in polymer membranes
follow complex mechanisms due to the nature of the water
Nitrogen
molecule. Water molecules are particularly small and have
a strong tendency to form hydrogen bonds between Nitrogen barrier properties of PLA films have also been
themselves and with other polar groups. Yoon et al.[161] investigated.[5] The value reported at 30 8C was 1.21
and Siparsky et al.[162] reported that water molecules found 1017 kg m/m2 s Pa, with an activation energy of
in a PLA matrix followed the water-cluster model rather 11.2 kJ mol1.
than the solution-diffusion model. They did not observe
variation of the diffusion coefficient with an increase in the
Organic Compounds (Ethyl Acetate and D-Limonene)
crystallinity of PLLA, which means that the water molec-
ules were associated with each other and formed clusters Permeability, diffusion and solubility coefficients of
TM
through preferential binding via hydrogen bonding. The D-limonene in PLA were reported for NatureWorks
[165]
water molecules are not highly soluble in the polymer and PLA. The permeability coefficient for D-limonene was
lower than 1 1018 kg m/m2 s Pa. Auras[108] also re-
ported similar values at 45 8C, with a partial pressure of
258 Pa. A diffusion coefficient and a permeability coef-
ficient lower than 1018 m2 s1 and 1018 kg m/m2 s
Pa, respectively, were found. PLA is a very good barrier to
D-limonene and is comparable to PET and Nylon-6.
In addition, Auras[108] studied the barrier of PLA to ethyl
acetate. A representative plot of the weight gain as a
function of time for the sorption of ethyl acetate by PLA
films is presented in Figure 13.
To reach equilibrium sorption required more than 30 d.
The diffusion, solubility and permeability coefficients
obtained from gravimetric experiments at 45 8C and 30 8C
are presented in Table 14.
As was predicted using the solubility parameters, ethyl
Figure 12. Water vapor permeability coefficient of poly(98% L- acetate is outside the solubility region of PLA. The solu-
lactide) as a function of %RH. Error bars represent cumulative bility coefficients for ethyl acetate in PLA can be consi-
imprecision in measurements. dered very low and are comparable to those of PET.
Table 15. Grease resistance of PLA coated paper according to

TAPPI T507, adapted from Gruber and O’Brien.[17]
Grease or Oil 23 8C no press 55 8C with press
Mineral Oil >120 h >24 h

Olive Oil >120 h >24 h
Oleic Acid >120 h >24 h
Butter >120 h >24 h
Studies of total and specific migration have been carried

out by Conn et al.[40] and Auras.[108] Poly(98% L-lactide)
stored for 15 d at 40 8C with two different food simulants,
10% ethanol and 95% ethanol, showed that the total amount
of food contact substances (FCS) that migrate from PLA
Figure 13. Sorption profile for ethyl acetate in PLA at 30 8C, polymer in simulant is lower than the average daily intake of
p ¼ 3 030 Pa. PLA initial weight 150 mg. lactic acid from all proposed uses as indirect food additives
(22 mg per day).[108] Total migration from the PLA is
12.9 mg kg1 of food in contact with the film. This total
Grease Resistance migration value is lower than the amount of lactic acid
present in a kilogram of yogurt (10 g/kg) or beef (9 g/kg)
Gruber and O’Brien[17] reported a higher resistance to
and it is less than the average dietary intake of lactic acid by
aliphatic molecules such as oils and terpenes in papers
infants. A related study of lactic acid migration can be
coated with PLA films. Paper coated with PLA did not fail
found elsewhere.[40] The amount of lactic acid and its deri-
by grease penetration after 120 h of testing at 55 8C,
vatives that migrates to ethanol solutions from PLA poly-
although paper coated with LDPE failed in just 10 h.[17]
mers was much lower than any of the current average
Table 15 indicates the resistance of PLA coated paper to
dietary lactic acid intake values reported by the Food and
different compounds.
Drug Administration, the US Department of Agriculture,
the European Community’s Scientific Committee on
Food and the Japanese Standards of Food Additives.
Migration
PLA polymers can be considered safe for their intended
Migrants from PLA may include lactic acid, lactoyllactic use in fabricating articles for contact with food. Any intake
acid, other small oligomers of polylactide and lactide. of potential migrants from PLA other than lactic acid will
Lactic acid is of primary interest because the other species be in very small amounts and these will hydrolyze to
are expected ultimately to hydrolyse to lactic acid. Scheme 5 lactic acid.
shows the chemical equilibria between lactic acid, its linear
dimer, trimer and lactide.
Degradation of PLA
Table 14. Ethyl acetate permeability, diffusion and solubility Biodegradation
coefficients for poly(98% L-lactide) at 45 8C and 30 8C.
PLA degrades primarily by hydrolysis, after several months
Temperature 45 30 exposure to moisture. Polylactide degradation occurs in two
8C stages. First, random non-enzymatic chain scission of the
ester groups leads to a reduction in molecular weight. This
Temperature 25 15 0 step can be accelerated by acids or bases and is affected by
Generated both temperature and moisture levels.[23] Embrittlement of
8C the polymers occurs in this step with a reduction of the
Partial pressure 12 654 7 560 3 030 molecular weight to around 40 900 Daltons. Second, low
molecular weight PLA can diffuse out of the bulk polymer
Pa
P 1.22 1017 1.18 1018 5.34 1019 and be used by microorganisms, yielding carbon dioxide,
water and humus.[30]
kg m/(m2 s Pa) In the first step, PLA degradability is driven by the
D 2.63 1015 2.81 1016 8.66 1017
hydrolysis and cleavage of the ester linkages in the polymer
m2/s backbone (Scheme 6), which is autocatalyzed by the carbo-
S 4.62 103 4.27 103 6.17 103 xylic acid end groups. The process follows first order
kg/(m3 Pa) kinetics.[166]
Scheme 5. Chemical structure of lactic acid and lactide, lactoyllactic acid and its trimer, adapted from
Conn et al.[40]
In the second step, the molecular weight is reduced until metal impurities from the catalyst, will affect the polymer
the lactic acid and low molecular weight oligomers are degradation rate.[1,3,15,21,23,39,95,119 –121,123,137,141,166–216]
naturally metabolized by microorganisms to yield carbon In general, high temperatures and humidity (50 to 60 8C)
dioxide and water (Figure 14). will cause PLA to degrade rapidly. For a detailed descrip-
Although the degradation process in PLA is a simple tion of the degradation process, see Snook.[30]
hydrolysis, the degradation rate can be affected by many Tsuji and collaborators[95,199,200] studied the hydrolysis
factors due to the complexity of the solid-liquid reaction of PLLA films at 37 8C in alkaline solution (pH 12)[199] acid
system. The polymer degradation rate is mainly determined solution (pH 2.0)[120] and phosphate-buffered solutions
by polymer reactivity with water and catalysts. Any factor (pH 7.4).[198] They reported that the hydrolysis of PLLA
which affects the reactivity and the accessibility, such as films proceeds mainly via a surface erosion mechanism in
particle size and shape, temperature, moisture, crystallinity, dilute alkaline solution[199] and mainly via a bulk erosion
% isomer, residual lactic acid concentration, molecular mechanism in a phosphate-buffered solution.[198] In acid
weight, molecular weight distribution, water diffusion and solution, the hydrolysis of PLLA proceeds homogeneously
along the film cross section mainly by the bulk erosion
mechanism. The durability of PLLA films in an acid
Figure 14. Biodegradation of PLA in 60 8C compost, adapted

Scheme 6. PLA hydrolysis and molecular weight loss. from Hartmann.[39]
medium is similar to that in a neutral medium. The ever, the worms cannot bioassimilate the polymer before
hydrolytic scission of PLLA chains occurs mainly in the the hydrolytic degradation process is completed and
amorphous area between the crystalline regions, irrespec- reduced the polymer to oligomers.
tive of the hydrolysis medium. They also reported that the PLA monolayer and PLA trilayer plastic films exposed to
overall hydrolysis rate of PLLA films decreases with incre- long wavelength UV (365 nm) at 55 8C and 10% RH for
asing initial crystallinity in alkaline solution and increases 8 weeks had an increase in the degradation rate compared to
with increasing crystallinity in phosphate-buffered solu- non-UV-treated samples. In addition, loss of physical pro-
tion. High-temperature hydrolysis was studied by Tsuji perties was observed two weeks earlier than for the non-UV-
et al.[121] They found that the high temperature hydrolysis of treated samples.[188] UV light has an enhancing effect on the
PLLA films proceeds homogeneously along the film cross- degradation of PLA plastic films.
section mainly via bulk erosion. PLLA hydrolysis at high Studies with PLA blends have been carried out by a
temperature takes place mainly in the amorphous region.[121] number of researchers,[187,218,219] who found that the
Tsuji and Ishida[217] reported that enzymatic and alkaline physical and morphologic properties of the blend play an
hydrolyses are strong enough to enhance the practical important role its degradation.
surface hydrophilicity of the PLLA films because of their The preparation and degradation of PLA nanocompo-
surface-erosion mechanisms. Gonzalez et al.[201] also sites was studied by Sinha Ray et al.[193] They found that a
studied the in vitro degradation of PLA microspheres under PLA-layered silicate nanocomposite produced by simple
humid environments at 37 8C. They found that the initial melt extrusion was biodegradable and that nanocomposites
smooth-surface microspheres were transformed into po- enhance biodegrability. During the first month, both the
rous particles during degradation at pH 7 and 37 8C, by a extent of molecular weight reduction and weight loss were
heterogeneous bulk degradation process, which accompa- almost the same for PLA and PLACN4, where CN4 indi-
nied a reduction in molecular weight and an increase in cates the presence of 4% nanocomposite particles. After a
crystallinity. On the other hand, studies done with bulk month there was a sharp weight loss for PLACN4 compared
PLLA[31] showed that the hydrolysis proceeds in two modes to that of PLA. They attributed the enhanced biodegrada-
– slow hydrolysis at the specimen surface and hydrolysis tion to the presence of the terminal hydroxylated edge
accelerated by formed and accumulated catalytic oligomers. groups on the silicate layers.[193,220] The authors also attri-
Composting studies were carried out by Weber[183] by bute the enhancement in the biodegradability to the incorpo-
storing PLA samples in biodegradation chambers. As a ration of organically modified synthetic fluorine mica.[194]
result, they recommended that a maximum of 10% PLA be
used in compost piles to prevent pH reduction of the pile.
Enzymatic
In addition, Gartiser et al.[187] compared the anaerobic
degradation of eight commercially available biodegradable Enzymes such as proteinase K, pronase and bromelain have
polymers according to different standards and found that been used to bring about hydrolysis of polylactide in vivo.
carbon dioxide is essential to the degradation process since However, enzymes are large molecules and are unable to
it enhances the growth of various anaerobic bacteria.[187] diffuse through the crystalline regions. As expected, little
Comparisons between laboratory and field exposure de- enzymatic degradation occurs at the beginning of the degra-
gradation have been done by Pometto and collabora- dation process. Enzymatic involvement can produce pores
tors.[189–191] They exposed PLA films in banana fields in and fragmentation, making more polymer regions acces-
Costa Rica and found that these PLA plastic films lost their sible to the enzymes.
mechanical properties faster than during exposure under
simulated conditions in the laboratory.[190] They also found
in vivo and in vitro
that degradation of PLA is enhanced by an increase in tem-
perature and relative humidity.[191] Finally, they predicted The in vivo and in vitro degradation have been evaluated for
that PLAwith an initial molecular weight of 180 000 Daltons polylactide surgical implants. In vitro studies showed that
would be visibly degraded in around 6 months at between the pH of the solution does play a role in the in vitro
29.6 8C and 23.4 8C and at a humidity of around 80%.[189] degradation and that an in vitro study can be used as a
A comparative study of the degradation of PLA and predictor of the in vivo degradation of PLA.[196] Further
starch-based materials was done by Gattin et al.[218] They studies of in vitro and in vivo degradation of PLA can be
reported that the nature of the degradation strongly depends found elsewhere.[3,6,9,11,13,177,182,196,197,211,214,221–226]
on the experimental conditions. A comparison between the
earthworm-induced degradation of two lactic acid stereo-
copolymers, 50/50 and 96/4/L/D poly(L-lactic-co-D-lactic
Burning
acid), was carried out by Alauzet et al.[186] They found that
high molar mass poly(lactic acid)s could be ingested by Burning of plastics materials with a high calorific value to
earthworms provided they were disintegrated first. How- obtain energy is an essential part of an overall waste
management scheme. Tight control of the burning plant is been blended with many different biodegradable polymers
pursued to achieve efficient combustion of the polymers such as polymers obtained from glycolic acid,[3,203,231–234]
with low gas emissions to ensure that no toxic gases are starch[57] and e-caprolactone.[3,60,66,118,160,168,177,235–243]
released. Therefore, polymers which have low gas emis- Investigations with starch polymers have been carried out
sions are preferred. Upon incineration, PLA burns with a by many researchers.[244] Park et al.[245] reported that the
clean blue flame, without generating any poisonous or glass transition temperature of both L-PLA and star-PLA/
corrosive gases.[137] cornstarch composites remained almost unchanged
although the crystallization was influenced. They found
an increase in the crystallization rate and in the enthalpies of
Recycling
crystallization and melting for PLA with starch contents
Few studies regarding the recycling of PLA have been above 5%.[245] Starch plays a role as a nucleating agent in
carried out. Both PLA and oriented PLA (oriented lactic PLA. Kim et al.[246] showed that PLA is incompatible with
acid) can be hydrolyzed with boiling water or steam to lactic starch granules. However, maleated PLA develops an
acid, which can be recycled back to the monomer. This interfacial adhesion with native corn starch.[244] Martin
could lead to molecular recycling and would allow the and Averous[150] reported better mechanical and physical
recycling of both manufacturing plant materials and post- properties with a different plasticizer than with thermo-
consumer packaging.[137] Tsuji et al.[195] showed that PLLA plastic starch, although they encouraged more research with
could be hydrolyzed at 180 8C to 350 8C for up to 30 min, starch due to its lower cost. The biodegradation of starch
obtaining L-lactic acid as the final product. and PLA based materials was studied and it was found that
temperature and relative humidity play a very important
role in the degradation process.[218] Wang et al.[219] found
Release that methylenediphenyl diisocyanate improves the inter-
facial interaction between PLA and granular starch. Ke and
Back in 1973, lactic acid and glycolic acid were proposed as
Sun[247] added poly(vinyl alcohol), PVOH, to the starch due
degradable matrices for the sustained release of bioactive
to its compatibility and then blended it with PLA. The final
substances. PLA has many advantages for this purpose,
result was that the tensile strength of the starch/PLA blends
which are that the polymeric matrix disappears innocu-
increased as the PVOH concentration increased up to 40%
ously, that degradation can be tailored by varying the
and decreased as PVOH molecular weight increased.[247]
copolymer composition and that controlled release devices
Both Wang[219] and Ke[247] found that gelatinized starch
are easily fabricated. Several publications[227–230] have
was responsible for an increase in tensile strength. Since
proposed different sustained-release devices, including
gelatinized starch absorbs water, the tensile strength and the
pellets, microspheres, microcapsules and cylinders. Subs-
elongation of the blend decreased as the starch moisture
tance release is done via zero or first order kinetics, depend-
content increased.[219,247] Further studies of starch-PLA
ing on design, diffusion or erosion and crystallinity. The
plastic foams indicated that the addition of PLA improved
release of the substance is complete in between one week to
the mechanical properties of the foams and reduced their bulk
several months, depending on the copolymer composition
densities and compressibilities.[248] The blends with 40%
and crystallinity, molecular weight, surface-to-volume ratio
PLA and 19% moisture produced a loose fill foam with the
and the service environment. Recently, Ahola et al.[228]
best physical characteristics and mechanical properties.[248]
investigated the release of ibuprofen from a PLA copolymer
Polymers made from e-caprolactone (CL) are excellent
with e-caprolactone. They found that the release of ibuprofen
drug permeation products. However, mechanical and phy-
varied with the initial shape and load of the specimen, and
sical properties need to be enhanced by copolymerization or
that the release of this material followed Fickian diffusion.
blending.[243] Ibuprofen release from polymers made from
Also, release of leuprolide have been carried out from D-PLA
e-caprolactone has proved successful due to their excellent
and L-PLA.[229] A linear release of leuprolide was obtained
drug permeation properties.[228] The addition of PLLA to
between day 6 and 25, with a continuous release for over 100
CL decreased the number densities of spherulites in PLLA
d. The molecular weight of PLA, and the D-PLA and L-PLA
and PCL films.[118] Moreover, the melting temperature of
complex ratios have an effect on the release ratio.
PLLA and PCL blends decreased by 3 and 0.5 8C, respec-
tively.[249] Liu et al.[184] found that the degradation of PLA
blends with poly(e-caprolactone) was selective, which
Copolymers, Blends, Composites
shows that the polymer blends exhibited well separated
and Nano-Composites
crystalline domains.
Polylactide blends are mixtures of different compositions of Blends of PLLA and poly(vinyl alcohol) were studied by
poly(L-lactide) and poly(D-lactide). Much research has been Tsuji and Muramatsu.[122] They showed that the tensile
done in this area and nearly all commercially available PLAs strength and Young’s modulus decreased with increase in
are a blend of stereoisomers. In addition, polylactides have the composition of PLLA.
Blends of poly(ethylene glycol), PEG, and poly(lactic Economic studies show that PLA is an economically
acid) showed an increase in the melting temperature of feasible material to use as a packaging polymer.[24] How-
around 40 8C for the PLA.[250] The molecular weight of the ever, due to its higher cost, the initial use of PLA as a
PEG affects the polymer morphology due to the enhanced packaging material has been in high value films, rigid
crystallinity of the longer PEG chains.[231] thermoforms, food and beverage containers and coated
Calcium phosphate composites with PLA showed an papers. Two of the pioneer companies in using PLA as a
increase in the flexural modulus and yield strength.[2] packaging material were Dannon and McDonald’s in
Poly(L-lactide)-clay blends made from a solvent-cast blend Germany in yoghurt cups and cutlery, respectively.[42,290]
showed a poor dispersion of clay in the mix. However, the In the last five years, the use of PLA as a packaging material
Young’s modulus of the blend increased with a small has increased all across Europe, Japan, and the USA, mainly
amount of clay.[251] in the area of fresh products where PLA is being used as a
Polylactide/layered silicate nanocomposites were inves- food packaging polymer for short shelf life products such as
tigated by Sinha Ray et al.[193,194,220,252–254] They suc- fruit and vegetables and package applications include
cessfully prepared a series of biodegradable PLA containers, drinking cups, sundae and salad cups, overwrap
nanocomposites using simple melt extrusion of PLA and and lamination films, and blister packages.[42,43,45,289,291–296]
organic modified layered silicate[220] and they reported the Currently, PLA is used in compostable yard bags[297] to
mechanical, physical and rheological properties of the encourage recycling and composting programs. In addition,
nanocomposites. new applications such as fibers,[22,77,113,298,299] tex-
Finally, a number of researchers investigated the use of tiles,[298,300] foamed articles[220,248,301] and paper coatings[29]
PLA blends and composites in comparison to commercial are being pursued. Commercial brands like Ingeo concentrate
biodegradable polymers for medical applications. A de- on commercializing fabrics made from polylactide poly-
tailed discussion of these investigations can be found mers.[298,302,303]
elsewhere.[3,9,16,32,70,124,170,173,202,215,231,233,234,238,255–284] Commercially available PLA films and packages can
provide better mechanical properties than polystyrene (PS)
and have properties comparable to those of poly(ethylene
Current Applications of Polylactides
terephthalate) (PET). The new, commercially available,
Polymers made of lactic acid achieved their first commercial PLA polymers promise to reduce the cost and to encourage
success as fiber materials for resorbable sutures. After this, a the use of PLA.[304] In the next ten years, PLA production
number of different prosthetic devices were developed. PLA and consumption is expected to increase substan-
has been widely studied for use in medical applications tially.[24,43,44,291,305–307]
because of its bioresorbability and biocompatible properties
in the human body.[1–6,8,11,12,14,16,32,54,196,224,225,260,285–288]
Since PLA manufacturing processes are lowering its Perspectives
production costs,[23,24] PLA may find use in different applica-
PLA polymers are becoming a cost-effective alternative to
tions for a broad array of products.
commodity petrochemical-based materials. The introduc-
The new Cargill Dow LLC polylactide plant in Blair, NB,
tion of PLA will encourage the use and expansion of
USA, which was inaugurated in April, 2002 promises to
agricultural based materials. As the PLA price drops and
help lower the cost and to encourage the use of PLA,
new facilities produce higher volumes of PLA, new
bringing to the market 140 000 tons of PLA per year.[289]
applications will be pursued. Although PLA is a relatively
The low-cost continuous process commercialized under the
new polymer, it is possible to manipulate its physical, mech-
tradename of NatureworksTM guarantees the production of
anical and barrier properties by changing its chemical
PLA for commercial applications.[17] NatureworksTM poly-
composition, and varying its molecular characteristics. It is
mers can be found in a variety of configurations (i.e. L-, D-,
also possible to blend PLA with other polymers, making it a
and meso-isomers) for a variety of applications.[147] Nature-
good biodegradable alternative for use in plastic packaging.
worksTM functional properties include improved folding
and sealing properties, high gloss and clarity, good grease
resistance, low heat sealing temperature and approval for Acknowledgement: The authors thank Kraft Foods for partially
food contact. supporting this project and Cargill Dow LLC for the polymer
Mitsui Chemical is conducting PLA business develop- samples.
ment under the commercial name of LACEA. LACEA
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Auras 2004 An Overview of Polylactides As Packaging Materials

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Auras 2004 An Overview of Polylactides As Packaging Materials

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Review 835

An Overview of Polylactides as Packaging Materials

Introduction obtained from a renewable agricultural source (corn);[25–27]

Scheme 1. Chemical structure of L and D-lactic acid (m.p. is

h1. If the lactic acid is used in pharmaceutical and food

Scheme 4. Constitutional unit of polylactide.

Scheme 3. Chemical structures of LL-, meso- and DD-lactides

Figure 2. Current production process for PLA, adapted from Gruber.[48]

Space Group Chain Orientation N. of Helical a b c a b g

Polymer n exp. n calculated

Lorentz and Lorentzb) Gladstone and Dalec) Vogeld)

Polyethylene 1.490a) 1.479 1.478 1.469

where Kg is the nucleation constant, s the lateral surface

Surface Energy Poly(98% L-lactide)a) 42 45b)

Figure 8. DMA curves of poly(98% L-lactide) (wc ¼ 40%)

Poly(lactic acid) Mark-Houwink constant Solvent

PLLA [Z] ¼ 5.45  104 Mv0.73 25 8C in chloroform[33,97]

Tensile strength 59 66 44 Density in solution[152] 10.25 0.16

Poly(98% L-lactide)a) Poly(94% L-lactide)a) PS Biaxial PET

Tensile yield stress 72 65 84 74 55–82 275

Figure 10. Volume dependent cohesion parameter (dv) versus

Material Water Activity P0  1014 EP D0  1012 ED S0  103 DHS

kg m/m2 s Pa kJ mol1 m2 s1 kJ mol1 kg/m3 Pa kJ mol1

PET 0.0 6.2 30.3 6.6 11.8 9.6 18.5

Table 15. Grease resistance of PLA coated paper according to

Grease or Oil 23 8C no press 55 8C with press

Mineral Oil >120 h >24 h

Studies of total and specific migration have been carried

Figure 14. Biodegradation of PLA in 60 8C compost, adapted

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PLLA [Z] ¼ 5.45 104 Mv0.73 25 8C in chloroform[33,97]

Material Water Activity P0 1014 EP D0 1012 ED S0 103 DHS